Sulphonic acids of the 5-oxo imidazoline series



Patented Sept. 18, 1 945 SULPHONIC ACIDS OF THE 5-OXO IMIDAZOLINE SERIESOskar Huppcrt, Chicago, 111.

No Drawing. Application March 3, 1941, Serial No. 381,545

1*!) Claims.

This invention relates to new sulphonic acids, their salts and esters,particularly to artificial protein fibers containing the same wherebyimprovements in wet strength, lustre and resistance to swelling result.

The new compounds have in their acid form the general formula:

wherein It indicates hydrogen, alkyl, aryl-alkyl or a heterocyclieradical and it indicates a numher from to 287. (For the specific term Rsee: "Des Protein und seine stereoisoineien Modifikatlonen. ChemischePhysik und Biochemie," page 17, picture IV, by Huppert, Vienna 1933,Chemical Abstracts 23, 3244.)

In my United States Patent Number 2,112,210 and in my co-pendingapplication Serial Number 378,774, filed February 13, 1941; I describedthiohydantoin disulphides, substituted in the nucleus in position 3 and5, prepared from proteins and- The compounds of the present inventioncan also be considered as derivatives of imidazoline and are -oxoimidazoline sulphonic acid-2 coma pounds substituted in the l and 4positions.

In the following formula the Formula A shows the numbering for thehydantoin ring and Formula B shows the numbering when considering thering as the lmidazoline.

R-CH-N 5 s 2 c-soin 4 a I o=c-- 1, I

R-CH-N 4 5 l 2 c-som (B) -the elasticity and flexibility of such fibers.

The compounds of the present invention possess very resistant sulphonicgroups and have specific detergent and textile finishing properties.They show a great aiiinity for protein fibers such as artificial fibers,wool, and the like and increase For instance, if artificial proteinfibers which have been prepared by first spinning into the coagulatingbath, stretching, hardening, washing, impregnating with quaternaryammonium compounds over-baking and drying, are treated with thecompounds of the present invention the relatively brittle fibers arerendered much more flexible and useful.

Instead of impregnating formed fibers with solutions of the sulphonicacids of thepresent invention fibers containing the protein disulphideprepared according to United States Patent No. 2,112,210 may be treatedwith hydrogen peroxide to convert the protein thiohydantoin disulphidesinto the corresponding sulphonic acids in. situ. By such a procedure thewet strength of the fiber is increased and the swelling decreased.

The salts of these sulphonic acids, particularly those of the alkali-,aluminum-, zinc-, chromemetals, amine bases can be prepared in the usualmanner.

The sulphonic acids and their salts are all soluble in water and arecapillary active and hence these products and their esters with highfatty alcohols can be used as detergents, as protective colloids, aswetting, dispersing emulsifying and softening agents, for improving dyefastness.

Certain sulphonic acids, manufactured from alpha amino acids, forinstance, from tyrosine, according to this invention, are excellentedible dyes, soluble in water and alcohol, and can be used in the foodand baking industry. (The dough, for instance, can be coloured withthese products as they are yellow like the egg-yolk.) Furthermore thesedyes are useful for colouring drugs, cosmetics and fats.

These compounds can be used in the textile, leather, fat andpharmaceutical industry and as insecticides and fungicides.

Especially these sulphonic acids can be used as dyestufI-preparations tochange the fibers in such a manner that they can be coloured withspecial dyestuffs.

i- Example 1 M liters water are poured over 1000 g. technical gelatineand the mixture is allowed to stand and swell over night. One obtainsthereby a gelatine solution of 10%. g. lime hydrate, dispersed in water,are added. The mixture is heated for one hour under vigorous stirringand then filtered. 64 cc. carbon disulphide are added under vigorousstirring at a temperature of 40 C. and

sulphurated for half an hour.. The excess of the carbon disulphide isremoved by heating to 80 C. One obtains a solution of Leukothiogelatine.Then '70 g. manganese dioxide are added under vigorous stirring andboiled for about 20 to 30 minutes until the solution becomes blood-redwith a shine into purple. The solution is now allowed to stand, decantedof the manganese dioxide and filtered. Afterwards 15.5 g. sulphuric acidare added to the red solution, care being taken against foaming. Thecolour turns from red to yellow. One trie with Congo paper for the bluecolour. This reaction takes place at about the boiling temperature. Thegypsum is then filtered after 4 hours. Now 3 cc. acetic acid (80%) and2500 cc. hydrogen peroxide (3%) are successively added to the solutionand boiled for half an hour. By evaporation to dryness on a drum dryerone obtains the sulphonic acid of the hydantoin.

Example 2 181 g. tyrosine are dissolved in 1200 cc. water. 80 g. sodiumhydroxide are added and the solution is warmed to 40 C. and filtered. 80cc. car'- bon disulphide are added to the solution and boiled underreflux for one hour with agitation at 45 C. Thereafter the excess of thecarbon disulphide is removed and the solution is heated to 70 C. Now 70g. manganese peroxid are added and the solution is held under stirringat 90C. for 15 minutes. The manganese peroxide is filtered and theorange coloured solution of the (4 oxybenzyl) 2 thiohydantoin 3 (4oxybenzyl) acetic acid disulphide is obtained as the sodium salt. 80 g.sulphuric acid and 40 g. acetic acid (80%) are added to the solutionwhich is then warmed to 40 C. Now 140 cc. hydrogen peroxide (30%) areadded to the solution, which is warmed slowly until boiling and thenboiled for minutes. By evapouration one obtains the 2 sulphonic acid ofthe 5 p.oxybenzyl-hydantoin 3 p.oxybenzy1 acetic acid in crystals, afterone has extracted the residue with boiling alcohol.

Example 3 Artificial fibers, spun from mixtures of caseinthiohydantoin-disulphide and urea are soaked at a temperature of 40 C.,after hardening, washing, impregnating with quaternary ammoniumcompounds, drying and baking, in an aqueous bath containing 5% by weightof the aluminum salt of the hydantoiri-gelatose-sulphonic-acid ofExample 1. After 10 minutes the fibers are takenout of the bath anddried. They have been prepared in such a manner that they have then 4that what I claim is:

1. The process which.comprises oxidizing disulphides selected from theclass having the formula with hydrogen peroxide to form the sulphonicacids having the formula a-cn-N o-soln rm co-Nn-',cna).coon

in which R is a group selected from the class consisting of hydrogenatoms, aliphatic, aliphatic-aromatic and heterocyclic radicals found Ina-amino acids, and a: is a number from 0 to 287.

2. The compound oi. the following formula, prepared from tyrosine:

HOCcHr-CHgCH-N C-SOt 3. A protein fiber containing a sulphonic compoundselected from the class consisting of sulphonic acids obtainable byoxidizing with hydrogen peroxide the disulphide iormed by treating anamino-compound selected from the class consisting of proteins andalpha-amino acids with carbon disulphide at a hydroxyl ion concentrationnot exceeding that of an aqueous solution of calcium hydroxide andoxidizing the thus sulphurized compound to form the disulphide, andsalts and esters of said sulphonic acids.

4. A protein fiber containing the sulphonic acid oxidation productresulting from treating a thiohydantoin disulphide with hydrogenperoxide.

5. A protein fiber containing the sulphonic acid" oxidation productresulting from treating a thiohydantoin protein disulphide withhydrogenperoxide.

6. A protein fiber according to claim 3 in which the disulphide isprepared from alpha-amino acids.

7. The process of treating protein fibers which comprises incorporatingin the fiber a sulphonic compound selected from the class consisting ofsulphonic acids obtainable by oxidizing with hydrogen peroxide thedisulphide formed by treating amino compounds selected from the classconsisting of proteins and amino acids with carbon disulphide at anhydroxyl ion concentration not exceeding that of a solution of calciumhydroxide and oxidizing the thus sulphurlzed product to form thedisulphide, and salts and esters of said sulphonic acids.

8. Compounds selected from the class consisting of (1) sulphonic acidshaving the formula R-C-N o-sosi HR (do-Nn-cnapcoon in which R'is a groupselected from the class consisting of hydrogen atoms, aliphatic,aliphatic aromatic and heterocyclic radicals found in 0: amino acids andat is a member from 0 to 287, (2) salts thereof, and (3) esters thereof.

9. The compounds of claim 8 in which a: is 0. 10. The compounds of claim8 in which a: is greater than 0. I

OSKAR HUPPER'I.

